Phthalocyanine compounds, ink compositions comprising said compounds, and printing process therewith

ABSTRACT

A process for forming an image on a substrate comprising applying a composition comprising: (a) a compound of Formula (1) and salts thereof, wherein: M is Cu or Ni; Pc represents a phthalocyanine nucleus of Formula (2); R 1 , R 2  and R 3  independently are H or optionally substituted C 1-4 alkyl; R 4  is optionally substituted C 1-4 -hydroxyalkyl; x is greater than 0 and less than 1.8; y and z are both greater than 0; and the sum of (x+y+z) is 2.4 to 4.5: and (b) a liquid medium: thereto by means of an ink jet printer. Also compositions, inks, compounds and ink jet printer cartridges

This invention relates to a an ink-jet printing process, to compositionsand inks suitable for use in this process, to novel compounds from whichthese compositions and inks may be prepared, to printed substrates andto ink-jet printer cartridges.

Ink-jet printing is a non-impact printing technique in which droplets ofink are ejected through a fine nozzle onto a substrate without bringingthe nozzle into contact with the substrate.

There are many demanding performance requirements for dyes and inks usedin ink-jet printing. For example they desirably provide sharp,non-feathered images having good water, light and ozone fastness andoptical density. The inks are often required to dry quickly when appliedto a substrate to prevent smudging, but they should not form a crustover the tip of an ink-jet nozzle because this will stop the printerfrom working. The inks should also be stable to storage over timewithout decomposing or forming a precipitate that could block the fineprinter nozzles.

Dyes containing a single copper phthalocyanine group and their use inink-jet printing are known. For example, C.I. Direct Blue 199 and C.I.Direct Blue 86 are used as colorants in commercial ink-jet printinginks. There are also newer phthalocyanines such as those described inU.S. Pat. No. 6,149,722. However, there is a continuing need to providecolorants having superior properties in ink-jet printing inks.

A particular problem for photorealistic quality printing is that ofpermanence, that is the ability of the colourants used in producing aphotographic print to retain their colour properties over a number ofyears. A key factor contributing to the poor permanence of prints is thequenching of printed colorants by atmospheric pollutants, such as ozone.

We have now found that certain cyan colorants when used in ink-jetprinting processes yield prints with improved permanence and especiallyimproved ozone-fastness.

Thus, according to the present invention there is provided a process forforming an image on a substrate comprising applying a composition whichcomprises:

-   (a) a compound of Formula (1) and salts thereof:

wherein:

-   -   M is Cu or Ni;    -   Pc represents a phthalocyanine nucleus of Formula (2);

-   -   R¹, R² and R³ independently are H or optionally substituted        C₁₋₄alkyl;    -   R⁴ is optionally substituted C₁₋₄-hydroxyalkyl;    -   x is greater than 0 and less than 1.8;    -   y and z are both greater than 0; and    -   the sum of (x+y+z) is 2.4 to 4.5: and

-   (b) a liquid medium:    thereto by means of an ink-jet printer.

The ink-jet printer preferably applies the composition to the substratein the form of droplets that are ejected through a small orifice ontothe substrate. Preferred ink-jet printers are piezoelectric ink-jetprinters and thermal ink-jet printers. In thermal ink-jet printers,programmed pulses of heat are applied to the ink in a reservoir by meansof a resistor adjacent to the orifice, thereby causing the ink to beejected from the orifice in the form of small droplets directed towardsthe substrate during relative movement between the substrate and theorifice. In piezoelectric ink-jet printers the oscillation of a smallcrystal causes ejection of the ink from the orifice. Alternately the inkcan be ejected by an electromechanical actuator connected to a moveablepaddle or plunger, for example as described in International PatentApplication WO 00/48938 and International Patent Application WO00/55089.

The substrate is preferably paper, plastic, textile, metal or glass,more preferably paper, an overhead projector slide or a textilematerial, especially paper.

Preferred papers are plain, treated or coated papers which may have anacid, alkaline or neutral character.

Photographic quality paper is particularly preferred.

Preferably in the compound of Formula (1) R¹, R² and R³ independentlyare H or methyl, more preferably in the compound of Formula (1) R¹, R²and R³ are all H.

In the compound of Formula (1) R⁴ may comprise more than 1 hydroxygroup, although preferably R⁴ comprises a single hydroxy.

Preferably in the compound of Formula (1) R⁴ is unsubstitutedC₁₋₄-hydroxyalkyl, more preferably C₂-hydroxyalkyl.

Preferred optional substituents which may be present on R¹, R², R³ andR⁴ are independently selected from: optionally substituted alkoxy(preferably C₁₋₄-alkoxy), optionally substituted aryl (preferablyphenyl), optionally substituted aryloxy (preferably phenoxy), optionallysubstituted heterocyclic, polyalkylene oxide (preferably polyethyleneoxide or polypropylene oxide), carboxy, phosphato, sulpho, nitro, cyano,halo, ureido, —SO₂F, hydroxy, ester, —NR⁵R⁶, —COR⁵, —CONR⁵R⁶, —NHCOR⁵,carboxyester, sulphone, and —SO₂NR⁵R⁶, wherein R⁵ and R⁶ are eachindependently H or optionally substituted alkyl (especially C₁₋₄-alkyl).Optional substituents for any of the substituents described for R¹, R²,R³ and R⁴ may be selected from the same list of substituents.

It is especially preferred that in the compound of Formula (1) that R¹,R² and R³ are all H and R⁴ is C₁₋₄-hydroxyalkyl, particularly —CH₂CH₂OH.

Preferably in the compound of Formula (1) x is greater than 0 and lessthan 1.5, more preferably x is greater than 0 and less than 1.2,especially x is greater than 0.05 and less than 1.0, more especially xis greater than 0.05 and less than 0.8 and particularly x is greaterthan 0.05 and less than 0.5.

Preferably in the compound of Formula (1) the sum of y+z is in the rangeof from 2.4 to 4.2, more preferably 2.7 to 4.1.

In the compound of Formula (1) the sum of (x+y+z) is preferably 3.5 to4.5, more preferably the sum of (x+y+z) is 3.8 to 4.2 and especially thesum of (x+y+z) is 4.0.

The values for x, y and z in compounds of Formula (1) all representstatistical averages.

The substituents represented by x, y and z may be present on anysusceptible position on the phthalocyanine ring system.

In one preferred embodiment it is provided that the compound of Formula(1) is not of formula

Acid or basic groups on the compounds of Formula (1), particularly acidgroups, are preferably in the form of a salt. Thus, the Formulae shownherein include the compounds in free acid and in salt form.

Preferred salts are alkali metal salts, especially lithium, sodium andpotassium, ammonium and substituted ammonium salts (including quaternaryamines such as ((CH₃)₄N⁺) and mixtures thereof. Especially preferred aresalts with sodium, lithium, ammonia and volatile amines, more especiallysodium salts. The compounds may be converted into a salt using knowntechniques.

The compounds of Formula (1) may exist in tautomeric forms other thanthose shown in this specification. These tautomers are included withinthe scope of the present invention.

The compounds of Formula (1) may be prepared by condensing copper ornickel phthalocyanine carrying sulphonyl chloride groups and sulphonicacid groups with compounds of formula HNR¹R² and HNR³R⁴ wherein R¹, R²,R³ and R⁴ are as hereinbefore defined. Many compounds of formula HNR¹R²and HNR³R⁴ are commercially available, for example ammonia andethanolamine, other made be readily prepared by a person of ordinaryskill. The condensation is preferably performed in water at a pH above7. Typically the condensation is performed at a temperature of 30 to 70°C. and the condensation is usually complete in less than 24 hours. Thecompounds of formula HNR¹R² and HNR³R⁴ may be used as a mixture orcondensed sequentially with the said phthalocyanine compound.

Copper and nickel phthalocyanines carrying sulphonyl chloride groups andoptionally sulphonic acid groups may be prepared by chlorosulphonatingcopper or nickel phthalocyanine, e.g. using chlorosulphonic acid andoptionally a chlorinating agent (e.g. POCl₃, PCl₅ or thionylchloride).

Preferred compositions comprise:

-   -   (a) from 0.01 to 30 parts of a compound of Formula (1); and    -   (b) from 70 to 99.99 parts of a liquid medium.

The number of parts of component (a) is preferably from 0.1 to 20, morepreferably from 0.5 to 15, and especially from 1 to 5 parts. The numberof parts of component (b) is preferably from 99.9 to 80, more preferablyfrom 99.5 to 85, especially from 99 to 95 parts.

Preferably component (a) is completely dissolved in component (b).Preferably component (a) has a solubility in component (b) at 20° C. ofat least 10%. This allows the preparation of liquid dye concentratesthat may be used to prepare more dilute inks and reduces the chance ofthe dye precipitating if evaporation of the liquid medium occurs duringstorage.

Preferred liquid media include water, a mixture of water and organicsolvent and organic solvent free from water.

When the medium comprises a mixture of water and organic solvent, theweight ratio of water to organic solvent is preferably from 99:1 to1:99, more preferably from 99:1 to 50:50 and especially from 95:5 to80:20.

It is preferred that the organic solvent present in the mixture of waterand organic solvent is a water-miscible organic solvent or a mixture ofsuch solvents. Preferred water-miscible organic solvents includeC₁₋₆-alkanols, preferably methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol andcyclohexanol; linear amides, preferably dimethylformamide ordimethylacetamide; ketones and ketone-alcohols, preferably acetone,methyl ether ketone, cyclohexanone and diacetone alcohol; water-miscibleethers, preferably tetrahydrofuran and dioxane; diols, preferably diolshaving from 2 to 12 carbon atoms, for example pentane-1,5-diol, ethyleneglycol, propylene glycol, butylene glycol, pentylene glycol, hexyleneglycol and thiodiglycol and oligo- and poly-alkyleneglycols, preferablydiethylene glycol, triethylene glycol, polyethylene glycol andpolypropylene glycol; triols, preferably glycerol and 1,2,6-hexanetriol;mono-C₁₋₄-alkyl ethers of diols, preferably mono-C₁₋₄-alkyl ethers ofdiols having 2 to 12 carbon atoms, especially 2-methoxyethanol,2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol,2-[2-(2-methoxyethoxy)ethoxy]ethanol,2-[2-(2-ethoxyethoxy)-ethoxy]-ethanol and ethyleneglycol monoallylether;cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone,N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; cyclicesters, preferably caprolactone; sulphoxides, preferably dimethylsulphoxide and sulpholane. Preferably the liquid medium comprises waterand 2 or more, especially from 2 to 8, water-miscible organic solvents.

Especially preferred water-miscible organic solvents are cyclic amides,especially 2-pyrrolidone, N-methyl-pyrrolidone and N-ethyl-pyrrolidone;diols, especially 1,5-pentane diol, ethyleneglycol, thiodiglycol,diethyleneglycol and triethyleneglycol; and mono-C₁₋₄-alkyl andC₁₋₄-alkyl ethers of diols, more preferably mono-C₁₋₄-alkyl ethers ofdiols having 2 to 12 carbon atoms, especially2-methoxy-2-ethoxy-2-ethoxyethanol.

Examples of further suitable liquid media comprising a mixture of waterand one or more organic solvents are described in U.S. Pat. No.4,963,189, U.S. Pat. No. 4,703,113, U.S. Pat. No. 4,626,284 and EP4,251,50A.

When the liquid medium comprises an organic solvent free from water,(i.e. less than 1% water by weight) the solvent preferably has a boilingpoint of from 30° to 200° C., more preferably of from 40° to 150° C.,especially from 50 to 125° C. The organic solvent may bewater-immiscible, water-miscible or a mixture of such solvents.Preferred water-miscible organic solvents are any of thehereinbefore-described water-miscible organic solvents and mixturesthereof. Preferred water-immiscible solvents include, for example,aliphatic hydrocarbons; esters, preferably ethyl acetate; chlorinatedhydrocarbons, preferably CH₂Cl₂; and ethers, preferably diethyl ether;and mixtures thereof.

When the liquid medium comprises a water-immiscible organic solvent,preferably a polar solvent is included because this enhances solubilityof the compound in the liquid medium. Examples of suitable polarsolvents include C₁₋₄-alcohols.

In view of the foregoing preferences it is especially preferred thatwhere the liquid medium is an organic solvent free from water itcomprises a ketone (especially methyl ethyl ketone) and/or an alcohol(especially a C₁₋₄-alkanol, more especially ethanol or propanol).

The organic solvent free from water may be a single organic solvent or amixture of two or more organic solvents. It is preferred that when themedium is an organic solvent free from water it is a mixture of 2 to 5different organic solvents. This allows a medium to be selected thatgives good control over the drying characteristics and storage stabilityof the ink.

Liquid media comprising an organic solvent free from water areparticularly useful where fast drying times are required andparticularly when printing onto hydrophobic and non-absorbentsubstrates, for example plastics, metal and glass.

The liquid media may also contain additional components conventionallyused in ink-jet printing inks, for example viscosity and surface tensionmodifiers, corrosion inhibitors, biocides, kogation reducing additivesand surfactants which may be ionic or non-ionic.

Although not usually necessary, further colorants may be added to thecomposition to modify the shade and performance properties. Examples ofsuch colorants include C.I.Direct Yellow 86, 132, 142 and 173;C.I.Direct Blue 199, and 307; C.I.Food Black 2; C.I.Direct Black 168 and195; C.I.Acid Yellow 23; and any of the dyes used in ink-jet printerssold by Seiko Epson Corporation, Hewlett Packard Company, Canon Inc. &Lexmark International. Addition of such further dyes can increaseoverall solubility leading to less kogation (nozzle blockage) for theresultant ink.

So that the compositions do not block the nozzles of the ink jet printerin use they are preferably prepared using high purity ingredients and/orby purifying the composition after it has been prepared. Suitablepurification techniques are well known, e.g. ultrafiltration, reverseosmosis, ion exchange and combinations thereof (either before or afterthey are incorporated in a composition according to the presentinvention). This purification results in the removal of substantiallyall of the inorganic salts and by-products resulting from its synthesis.Such purification assists in the preparation of a low viscosity aqueoussolution suitable for use in an ink-jet printer.

Preferably the composition has a viscosity of less than 20 cP, morepreferably less than 10 cP, especially less than 5 cP, at 25° C. Theselow viscosity compositions are particularly well suited for applicationto substrates by means of ink-jet printers.

Preferably the composition contains less than 500 ppm, more preferablyless than 250 ppm, especially less than 100 pm, more especially lessthan 10 ppm in total of divalent and trivalent metal ions (other thanany divalent and trivalent metal ions bound to a component of thecomposition). Free divalent and trivalent metals can form insolublecomplexes on storage that could block the ink-jet printer nozzles.

Preferably the composition has been filtered through a filter having amean pore size below 10 μm, more preferably below 3 μm, especially below2 μm, more especially below 1 μm. This filtration removes particulatematter that could otherwise block the fine nozzles found in many ink-jetprinters.

Preferably the composition contains less than 500 ppm, more preferablyless than 250 ppm, especially less than 100 pm, more especially lessthan 10 ppm in total of halide ions. High levels of halide ions cancause detrimental effects such as, for example, corrosion of metal partsin the ink-jet printer heads.

A second aspect of the invention provides a composition comprising:

-   (a) a compound of Formula (1) and salts thereof:

wherein:

-   -   M is Cu or Ni;    -   Pc represents a phthalocyanine nucleus of Formula (2);

-   -   R¹, R² and R³ independently are H or optionally substituted        C₁₋₄alkyl;    -   R⁴ is optionally substituted C₁₋₄-hydroxyalkyl;    -   x is greater than 0 and less than 1.8;    -   y and z are both greater than 0; and    -   the sum of (x+y+z) is 2.4 to 4.5; and

-   (b) a liquid medium which comprises water and an organic solvent or    an organic solvent free from water.

Preferred compositions are as described in the first aspect of theinvention.

Preferences for the compounds of Formula (1) are as described andpreferred in the first aspect of the invention.

The organic solvent in the mixture of water and organic solvent is aspreferred in the first aspect of the invention.

The organic solvent free from water is as preferred in the first aspectof the invention.

It is particularly preferred that the composition according to thesecond aspect of the invention is an ink-jet printing ink or a liquiddye concentrate. Concentrates are useful as a means for transportingcolorant and so minimising costs associated with drying the dye andtransporting excess liquid.

A third aspect of the present invention provides a compound of Formula(1) and salts thereof:

wherein:

-   -   M is Cu or Ni;    -   Pc represents a phthalocyanine nucleus of Formula (2);

-   -   R¹, R² and R³ independently are H or optionally substituted        C₁₋₄alkyl;    -   R⁴ is optionally substituted C₁₋₄-hydroxyalkyl;    -   x is greater than 0 and less than 1.8;    -   y and z are both greater than 0; and    -   the sum of (x+y+z) is 2.4 to 4.5:        provided that the compound of Formula (1) is not of formula

Compounds of Formula (1) are as preferred in the first aspect of theinvention.

The compounds of Formula (1) may be prepared as described in the firstaspect of the invention.

The compounds of Formula (1) have attractive, strong cyan shades and arevaluable colorants for use in the preparation of inkjet printing inks.They benefit from a good balance of solubility, storage stability andfastness to water and light. In particular they display excellent lightand ozone fastness. Furthermore they may be prepared from cheapintermediates, avoiding the complexity and expense which is involved inmanufacturing some of the more elaborate phthalocyanines.

A fourth aspect of the invention provides a composition which comprisesa compound of Formula (1) according to the third aspect of the inventionand a liquid medium. Preferred liquid media include water, a mixture ofwater and organic solvent and organic solvent free from water asdescribed in the first aspect of the invention.

A fifth aspect of the present invention provides paper, plastic,textile, metal or glass, more preferably paper, an overhead projectorslide or a textile material, especially paper more especially plain,coated or treated papers and particularly photographic quality paperprinted by means of a process according to the first aspect of theinvention, with a composition according to the second or fourth aspectsof the invention or with a compound according to the third aspect of theinvention.

A sixth aspect of the present invention provides an inkjet printercartridge comprising a chamber and an ink wherein the ink is in thechamber and the ink is as defined in the second or fourth aspects of thepresent invention.

The invention is further illustrated by the following Examples in whichall parts and percentages are by weight unless otherwise stated.

EXAMPLE 1

Preparation of the Following Dye Wherein x is 0.8 and (y+z) is 3.2:

Stage 1Preparation of:

Copper phthalocyanine (118.7 g: molar ratio 1) was added in portions toa mixture of stirred chlorosulphonic acid (310 ml: molar ratio 23) andphosphorous oxychloride (37.8 ml: molar ratio 2) while keeping thetemperature in the range of 50 to 60° C. The mixture was heatedgradually to 140° C., and kept at that temperature, with stirring, for 3hours. The reaction mixture was then poured onto a mixture of ice (3kg), water (1400 ml) and sodium chloride (160 g). The precipitate whichformed was collected by filtration at reduced pressure and washed with3% brine (500 ml) before being used in Stage 2.

Stage 2

Preparation of Title Dye:

Water (2 litre), ethanolamine (24.6 g, molar ratio 2) and 35% ammoniasolution (20 g: molar ratio 2) were mixed in a 5 litre beaker and thenplaced in an ice bath (pH=11.5, temperature 8° C.). The phthalocyaninesulphonyl chloride paste (molar ratio 1), resulting from stage 1 above,was slowly added to the mixture while the temperature was kept below 5°C. and the pH was maintained at pH 8 by the addition of 10% v/v sodiumhydroxide. The reaction mixture was left overnight at room temperatureand then heated at 40° C. for 4 hours. Sodium chloride (50% w/v) wasadded and the resultant precipitate was collected by filtration atreduced pressure and desalinated by dialysis to obtain the title dyewherein x is 0.8 and (y+z) is 3.2.

EXAMPLES 2 TO 9

Example 1 was repeated except that the molar ratios of POCl₃,ethanolamine and ammonia were as shown in Table 1.

EXAMPLES 10 TO 16

Stage 1

The method of Example 1, stage 1, was repeated except that the molarratio of POCl₃ used in each example was as shown in Table 1.

Stage 2

Water (1 litre) and ethanolamine (12 g, molar ratio 1) were mixed andthen placed in an ice bath. The phthalocyanine sulphonyl chloride pastes(molar ratio 1), prepared as described in stage 1 were slowly added tothe mixture while the temperature was kept below 5° C. and the pH wasmaintained at pH 8 by the addition of 10% v/v. ammonia solution. Thereaction mixture was left overnight at room temperature and then heatedat 40° C. for 4 hours. Sodium chloride (20% w/v) was added and theresultant precipitate was collected by filtration at reduced pressureand desalinated by dialysis to obtain the phthalocyanine dyes describedin Examples 10 to 16 of Table 1 below.

TABLE 1 POCl₃ Ethanolamine Ammonia Example (molar ratio) (molar ratio)(molar ratio) x y + z 2 2 4 2 0.1 4.0 3 2 6 2 0.1 4.0 4 2 2 4 1.1 3.0 52 2 6 1.0 3.0 6 2.5 2 4 0.4 3.4 7 2.5 4 2 0.2 3.6 8 2.5 2 6 0.2 3.4 92.5 2 2 0.6 3.2 10  1.5 1 AR 1.3 2.8 11  2 1 AR 0.8 3.2 12  2.5 1 AR 1.42.6 13  3 1 AR 0.8 3.2 14  3.5 1 AR 0.4 3.6 15  3.8 1 AR 0.4 3.8 16  1 1AR 0.7 3.4 AR - as required to adjust the pH is step (b) to pH 8.0.

COMPARATIVE EXAMPLE

The phthalocyanine dye:

was prepared as described in Example 1 of U.S. Pat. No. 6,149,722 whichpreparation is incorporated herein by reference.

EXAMPLES 17 TO 33

Preparation of Inks 1 to 16

The compounds of Examples 1 to 16 (3.5 g) were dissolved in 100 ml of aliquid medium consisting of 2-pyrrolidone/thiodiglycol/Sufynol™ 465 in aweight ratio of 5:5:1. In Table 2 below, Ink 1 contains the compound ofExample 1, Ink 2 the compound of Example 2 and so on.

Preparation of the Comparative Ink

The compound of the Comparative Example (3.5 g) was dissolved in 100 mlof a liquid medium consisting of 2-pyrrolidone/thiodiglycol/Sufynol™ 465in a weight ratio of 5:5:1.

EXAMPLE 34

Ozone Fastness

The Example Inks 1 to 16 and the Comparative Ink were printed onto avariety of papers using a Canon 5800™ IJ printer. The printed substratewas then assessed for ozone stability using an ozone test cabinet fromHampden Test Equipment. The test was carried out for twenty four hoursat 40° C. and 50% relative humidity in the presence of 1 part permillion of ozone. Fastness of the printed ink to ozone was judged by thedifference in the optical density before and after exposure to ozoneusing a Gretag MacBeth Spectrolino. Thus, the lower the % OD loss thegreater the ozone fastness. Results are shown below in Table 2 and theseclearly demonstrate that inks based on compounds of this inventiondisplay good ozone fastness.

TABLE 2 Ink Substrate % OD loss Ink 1 HP Premium Plus 2 Ink 1 CanonPR101 48 Ink 1 SEC Premium Photo 53 Ink 2 HP Premium Plus 0 Ink 2 CanonPR101 27 Ink 2 SEC Premium Photo 21 Ink 3 HP Premium Plus 0 Ink 3 CanonPR101 27 Ink 3 SEC Premium Photo 12 Ink 4 HP Premium Plus 2 Ink 4 CanonPR101 53 Ink 4 SEC Premium Photo 54 Ink 5 HP Premium Plus 3 Ink 5 CanonPR101 52 Ink 5 SEC Premium Photo 45 Ink 6 HP Premium Plus 2 Ink 6 CanonPR101 39 Ink 6 SEC Premium Photo 38 Ink 7 HP Premium Plus 3 Ink 7 CanonPR101 30 Ink 7 SEC Premium Photo 28 Ink 8 HP Premium Plus 2 Ink 8 CanonPR101 33 Ink 8 SEC Premium Photo 33 Ink 9 HP Premium Plus −1 Ink 9 CanonPR101 41 Ink 9 SEC Premium Photo 41 Ink 10 HP Premium Plus 2 Ink 10Canon PR101 43 Ink 10 SEC Premium Photo 45 Ink 11 HP Premium Plus 1 Ink11 Canon PR101 37 Ink 11 SEC Premium Photo 39 Ink 12 HP Premium Plus 4Ink 12 Canon PR101 55 Ink 12 SEC Premium Photo 56 Ink 13 HP Premium Plus3 Ink 13 Canon PR101 23 Ink 13 SEC Premium Photo 19 Ink 14 HP PremiumPlus 0 Ink 14 Canon PR101 17 Ink 14 SEC Premium Photo 12 Ink 15 HPPremium Plus 1 Ink 15 Canon PR101 15 Ink 15 SEC Premium Photo 7 Ink 16HP Premium Plus 2 Ink 16 Canon PR101 28 Ink 16 SEC Premium Photo 25Comparative Ink HP Premium Plus 4 Comparative Ink Canon PR101 71Comparative Ink SEC Premium Photo 64Further Inks

The inks described in Tables A and B may be prepared using the compoundsmade in Examples 1 to 16. Numbers quoted in the second column onwardsrefer to the number of parts of the relevant ingredient and all partsare by weight. The inks may be applied to paper by thermal or piezoink-jet printing.

The following abbreviations are used in Table A and B:

-   -   PG=propylene glycol    -   DEG=diethylene glycol    -   NMP=N-methylpyrollidone    -   DMK=dimethylketone    -   IPA=isopropanol    -   MEOH=methanol    -   2P=2-pyrollidone    -   MIBK=methylisobutyl ketone    -   P12=propane-1,2-diol    -   BDL=butane-2,3-diol    -   CET=cetyl ammonium bromide    -   PHO=Na₂HPO₄ and    -   TBT=tertiary butanol    -   TDG=thiodiglycol

TABLE A Dye Na Example Content Water PG DEG NMP DMK NaOH Stearate IPAMEOH 2P MIBK  1 2.0 80 5 6 4 5  2 3.0 90 5 5 0.2  3 10.0 85 3 3 3 5 1  42.1 91 8 1  5 3.1 86 5 0.2 4 5  6 1.1 81 9 0.5 0.5 9  7 2.5 60 4 15  3 36 10  5 4  8 5 65 20  10   9 2.4 75 5 4 5 6 5 10 4.1 80 3 5 2 10  0.3 113.2 65 5 4 6 5 4 6 5 12 5.1 96 4 13 10.8 90 5 5 14 10.0 80 2 6 2 5 1 415 1.8 80 5 15  16 2.6 84 11  5 14 3.3 80 2 10  2 6 15 12.0 90 7 0.3 314 5.4 69 2 20  2 1 3 3 15 6.0 91 4 5

TABLE B Dye Example Content Water PG DEG NMP CET TBT TDG BDL PHO 2P PI2 1 3.0 80 15 0.2 5  2 9.0 90 5 1.2 5  3 1.5 85 5 5  0.15 5.0 0.2  4 2.590 6 4  0.12  5 3.1 82 4 8 0.3 6  6 0.9 85 10  5 0.2  7 8.0 90 5 5 0.3 8 4.0 70 10  4 1 4 11   9 2.2 75 4 10  3 2 6 10 10.0 91 6 3 11 9.0 76 97 3.0  0.95 5 12 5.0 78 5 11  6 13 5.4 86 7 7 14 2.1 70 5 5 5 0.1 0.20.1 5 0.1 5 15 2.0 90 10  16 2 88 10 14 5 78 5 12 5 15 8 70 2 8 15 5 1410 80 8 12  15 10 80 10 

1. A process for forming an image on a substrate comprising applying acomposition which comprises: (a) a compound of Formula (1) and saltsthereof:

wherein: M is Cu or Ni; Pc represents a phthalocyanine nucleus ofFormula (2);

R¹ and R² are H; R³ is H or optionally substituted C₁₋₄alkyl; R⁴ isoptionally substituted C₁₋₄-hydroxyalkyl; x is greater than 0 and lessthan 1.2; y and z are both greater than 0; and the sum of (x+y+z) is 2.4to 4.5: and (b) a liquid medium: thereto by means of an ink-jet printer.2. A process according to claim 1 wherein in the compound of Formula (1)R¹, R² and R³ are all H.
 3. A process according to either claim 1 orclaim 2 wherein in the compound of Formula (1) R⁴ is unsubstitutedC₁₋₄-hydroxyalkyl.
 4. A process according to claim 3 wherein in thecompound of Formula (1) R⁴ is C₂-hydroxyalkyl.
 5. A process according toclaim 3 wherein in the compound of Formula (1) x is greater than 0.05and less than 1.0.
 6. A process according to claim 1 wherein in thecompound of Formula (1) x is greater than 0.05 and less than 0.5.
 7. Acomposition comprising: (a) a compound of Formula (1) and salts thereof:

wherein: M is Cu or Ni; Pc represents a phthalocyanine nucleus ofFormula (2);

R¹ and R²; R³ is H or optionally substituted C₁₋₄alkyl; R⁴ is optionallysubstituted C₁₋₄-hydroxyalkyl; x is greater than 0 and less than 1.2; yand z are both greater than 0; and the sum of (x+y+z) is 2.4 to 4.5; and(b) a liquid medium which comprises water and an organic solvent or anorganic solvent free from water.
 8. A composition according to claim 7wherein in the compound of Formula (1) R¹, R² and R³ are all H.
 9. Acomposition according to either claim 7 or claim 8 wherein in thecompound of Formula (1) R⁴ is unsubstituted C₁₋₄-hydroxyalkyl.
 10. Acomposition according to claim 9 wherein in the compound of Formula (1)R⁴ is C₂-hydroxyalkyl.
 11. A composition according to claim 7 wherein inthe compound of Formula (1) x is greater than 0.05 and less than 1.0.12. A composition according to claims 7 wherein in the compound ofFormula (1) x is greater than 0.05 and less than 0.5.
 13. A compound ofFormula (1) and salts thereof:

wherein: M is Cu or Ni; Pc represents a phthalocyanine nucleus ofFormula (2);

R¹, R² and R³ independently are H or optionally substituted C₁₋₄alkyl;R⁴ is optionally substituted C₁₋₄-hydroxyalkyl; x is greater than 0 andless than 1.0; y and z are both greater than 0; and the sum of (x+y+z)is 2.4 to 4.5.
 14. A compound according to claim 13 wherein in thecompound of Formula (1) R¹, R² and R³ are all H.
 15. A compoundaccording to either claim 13 or claim 14 wherein in the compound ofFormula (1) R⁴ is unsubstituted C₁₋₄-hydroxyalkyl.
 16. A compoundaccording to claim 15 wherein in the compound of Formula (1) R⁴ isC₂-hydroxyalkyl.
 17. A compound according to claims 13 wherein in thecompound of Formula (1) x is greater than 0.05 and less than 0.5.
 18. Acomposition which comprises a compound of Formula (1) according to claim13 and a liquid medium.
 19. A paper, plastic, textile, metal or glassmaterial printed by means of a process according to claim
 1. 20. Apaper, plastic, textile, metal or glass material printed with acomposition according to claim
 7. 21. A paper, plastic, textile, metalor glass material printed with a compound according to claim
 13. 22. Anink-jet printer cartridge comprising a chamber and an ink wherein theink is in the chamber and the ink is as defined in claim 7.